The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

Perrin, Jonathan; Rivard, Camille; Vielzeuf, Daniel; Laporte, Didier; Fonquernie, Claire; Ricolleau, A.; Cotte, Marine; Floquet, N.

doi:10.1016/j.gca.2016.10.017

Cited by 27 publications

(47 citation statements)

References 69 publications

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“…and from variations of organic matter (OM) content (see below). Carbon contents lower than 120,003 µg/g (the C content of inorganic calcite) may indicate the presence of sulfate substituting to carbonate ions as demonstrated in previous studies (Vielzeuf et al, 2013;Tamenori et al, 2014;Nguyen et al, 2014;Perrin et al, 2017).…”

Section: Hydrogen and Sulfur Measured By Oeasupporting

confidence: 51%

“…Hydrogen contents in the skeletons can be related to the amount of OM in the biomineral if all H is contained in the OM, and if the H content of the OM is known (Perrin et al, 2017). Concerning the first assumption, no evidence of hydrated Mg calcite in Corallium species has been found so far in Raman investigations (Merlin and Dele-Dubois, 1986).…”

Section: Hydrogen and Sulfur Measured By Oeamentioning

confidence: 99%

“…The positive correlation between Mg and Sr was explained by steric effects: a large cation (Sr) compensating the distortion produced in calcite by the introduction of small cation (Mg). The sulfur case is more complicated: it has been demonstrated that sulfur is present as sulfate ions (SO 4 2− ) substituting to carbonate ions (CO 3 2− ) in Corallium skeletons (Vielzeuf et al, 2013;Nguyen et al, 2014;Tamenori et al, 2014;Perrin et al, 2017). One would expect the lattice distortion related to the presence of a large anion (SO 4 2− larger than CO 3 2− ) to be compensated by the incorporation of a small cation such as Mg.…”

Section: Growth Kinetics and The Incorporation Of Elements In Calcitementioning

confidence: 99%

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Growth Kinetics and Distribution of Trace Elements in Precious Corals

et al. 2018

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The concentration and spatial distribution of major (Ca, Mg) and trace elements (Na, Sr, S, Li, Ba, Pb, and U) in different Corallium skeletons (C. rubrum, C. japonicum, C. elatius, C. konojoi) have been studied by electron microprobe (EMP) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). EMP data show positive Na-Mg and negative Na-S and Mg-S correlations in all skeletons. LA-ICPMS data display additional Sr-Mg, Li-Mg, and U-Mg positive correlations. Medullar zones in the skeletons, corresponding to fast growing zones, are systematically richer in Mg, Na, Sr, Li, and U and poorer in S than the surrounding slow growing zones. These spatial distributions are mostly interpreted in terms of growth kinetics combined with steric effects influencing the incorporation of impurities in biogenic calcites. This interpretation is in agreement with available experimental data on kinetic effects on the incorporation of elements in calcite. At a different scale, annual growth rings in annular slow growing zones show oscillations in Mg, Na, Sr, and S. These chemical oscillations probably result from growth rate variations: fast growth would produce rings enriched in Mg, Sr, and Na, while slow growth would produce rings enriched in Ca, S and organic matter. From previous studies in C. rubrum, the Mg-rich rings would develop during the spring to fall period while the S-rich rings would form immediately after (late fall and winter). Analytical traverses performed in annular zones of different Corallium skeletons indicate that Mg, Na, Sr, Li, and U decrease from core to rim. This observation indicates that radial growth rate decreases as the colony gets older. Contrary to Mg, Na, Sr, Li, S, and U, barium and lead concentrations are identical in medullar and annular zones and appear independent of growth kinetics. Thus, concentrations in Corallium skeletons could provide indications on Ba and Pb contents in the oceans. Barium and lead concentrations are higher in Mediterranean than in Pacific precious corals, these two elements can be used to discriminate C. rubrum from C. japonicum, and contribute enforcing regulations on the trade of precious corals.

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Section: Hydrogen and Sulfur Measured By Oeasupporting

confidence: 51%

Section: Hydrogen and Sulfur Measured By Oeamentioning

confidence: 99%

Section: Growth Kinetics and The Incorporation Of Elements In Calcitementioning

confidence: 99%

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Growth Kinetics and Distribution of Trace Elements in Precious Corals

et al. 2018

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“…Magnesium ions in the parent solution have been found to increase the coprecipitation of other elements (Okumura and Kitano, 1986). However, this is observed for alkali metal ions, which are in interstitial positions or substitute for Ca 2+ in the crystal lattice, while SO 2− 4 is hypothesized to exchange for CO 2− 3 ions (Pingitore et al, 1995;Perrin et al, 2017;Berry, 1998). Besides promoting coprecipitation, incorporation of magnesium in carbonate is suggested to cause strain on the crystal lattice, leading to distortion and an increase in the incorporation of other elements (Mucci and Morse, 1983).…”

Section: Calcite Precipitation and Physicochemical Conditionsmentioning

confidence: 99%

“…proxy tool box is the sulfur to calcium ratio (S/Ca) values of foraminiferal shells. In both abiogenic and biogenic carbonates, sulfur is mainly present in the form of SO 2− 4 , where it substitutes for CO 2− 3 (Pingitore et al, 1995;Perrin et al, 2017). S/Ca is correlated to the ratio of SO 2− 4 and CO 2− 3 in seawater in both inorganic carbonates (Fernández-Díaz et al, 2010) as well as in foraminiferal calcite (Paris et al, 2014;van Dijk et al, 2017a).…”

Section: Introductionmentioning

confidence: 99%

Coupled calcium and inorganic carbon uptake suggested by magnesium and sulfur incorporation in foraminiferal calcite

et al. 2019

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Abstract. Shell chemistry of foraminiferal carbonate proves to be useful in reconstructing past ocean conditions. A new addition to the proxy toolbox is the ratio of sulfur (S) to calcium (Ca) in foraminiferal shells, reflecting the ratio of SO42- to CO32- in seawater. When comparing species, the amount of SO42- incorporated, and therefore the S∕Ca of the shell, increases with increasing magnesium (Mg) content. The uptake of SO42- in foraminiferal calcite is likely connected to carbon uptake, while the incorporation of Mg is more likely related to Ca uptake since this element substitutes for Ca in the crystal lattice. The relation between S and Mg incorporation in foraminiferal calcite therefore offers the opportunity to investigate the timing of processes involved in Ca and carbon uptake. To understand how foraminiferal S∕Ca is related to Mg∕Ca, we analyzed the concentration and within-shell distribution of S∕Ca of three benthic species with different shell chemistry: Ammonia tepida, Bulimina marginata and Amphistegina lessonii. Furthermore, we investigated the link between Mg∕Ca and S∕Ca across species and the potential influence of temperature on foraminiferal S∕Ca. We observed that S∕Ca is positively correlated with Mg∕Ca on a microscale within specimens, as well as between and within species. In contrast, when shell Mg∕Ca increases with temperature, foraminiferal S∕Ca values remain similar. We evaluate our findings in the light of previously proposed biomineralization models and abiological processes involved during calcite precipitation. Although all kinds of processes, including crystal lattice distortion and element speciation at the site of calcification, may contribute to changes in either the amount of S or Mg that is ultimately incorporated in foraminiferal calcite, these processes do not explain the covariation between Mg∕Ca and S∕Ca values within specimens and between species. We observe that groups of foraminifera with different calcification pathways, e.g., hyaline versus porcelaneous species, show characteristic values for S∕Ca and Mg∕Ca, which might be linked to a different calcium and carbon uptake mechanism in porcelaneous and hyaline foraminifera. Whereas Mg incorporation might be controlled by Ca dilution at the site of calcification due to Ca pumping, S is linked to carbonate ion concentration via proton pumping. The fact that we observe a covariation of S and Mg within specimens and between species suggests that proton pumping and Ca pumping are intrinsically coupled across multiple scales.

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Microbial activity affects sulphur in biogenic aragonite

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Lange

Krause

et al. 2021

The Depositional Record

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Carbonates that exhibit obvious diagenetic alteration are usually excluded as archives in palaeoenvironmental studies. However, the potential impact of microbial alteration during early diagenesis is still poorly explored. To investigate the sensitivity of sulphur concentration, distribution, oxidation state and isotopic composition in marine aragonite to microbial alteration, Arctica islandica bivalves and Porites sp. corals were experimentally exposed to anaerobic microbial activity. The anoxic incubation media included a benthic bacterial strain Shewanella sediminis and a natural anoxic sediment slurry with a natural microbial community of unknown species. Combined fluorescence microscopy and synchrotron‐based analysis of the sulphur distribution and oxidation state enabled a comparison of organic matter and sulphur content in the two materials. Results revealed a higher proportion of reduced sulphur species and locally stronger fluorescence within the pristine bivalve shell compared to the pristine coral skeleton. Within the pristine bivalve specimen, reduced sulphur was enriched in layers along the inner shell margin. After incubation in the anoxic sediment slurry, this region revealed rust‐brown staining and a patchy S2‐ distribution pattern rather than S2‐‐layers. Another effect on sulphur distribution was rust‐brown coloured fibres along one growth line, revealing a locally higher proportion of sulphur. The δ34S value of carbonate‐associated sulphate remained largely unaffected by both incubation media, but a lower δ34S value of water‐soluble sulphate reflected the degradation of insoluble organic matter by microbes in both experiments. No significant alteration was detected in the coral samples exposed to microbial alteration. The data clearly identified a distinct sensitivity of organically bound sulphur in biogenic aragonite to microbial alteration even when ‘traditional’ geochemical proxies such as δ18OCARB or δ13CCARB in the carbonate did not show any effect. Differences in the intensity of microbial alteration documented are probably due to inherent variations in the concentration and nature of original organic compositions in the samples.

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The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

Cited by 27 publications

References 69 publications

Growth Kinetics and Distribution of Trace Elements in Precious Corals

Growth Kinetics and Distribution of Trace Elements in Precious Corals

Coupled calcium and inorganic carbon uptake suggested by magnesium and sulfur incorporation in foraminiferal calcite

Microbial activity affects sulphur in biogenic aragonite

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